Method for transforming and distilling hydrocarbons



oci. 2s, 1930;

A. A. F. `M. smc-n.15" 1,779,828 METHOD Fon TRANsFoRMING AND DISTILLING IYbR'ocARBoNs origina Filed July- 1e, 1920 5 sheets-sheet 1 @www 4MM Oct. 28, 1930. A. A. F. M. sl-:IGLE l 1,779,828

METHOD FOR TRANSFORMING AND DISTILLING' HYDROARBONS Original Filed July 16, 1920 5 sheets-sheet -2 Oct. 28, 1930. "A, A. F. M. sElGLE v1,779,828. METHOD FOR TRNSFORMING AND DISTILLING HYDROCRBONS I Original Filed July 16, 1 920 5 Sheets-Sheet 3 000191*- E .Ex/:ander JMW Oct. 28, 1930. A. A. F. u. 'SEIGLE' r 1,7795828' METHOD FOR TRANSKFORMING AND DISTILLING HYDROGARBONS I original Filed July le, 1920 5 sheets-sheet 4 Mmllmwwl@ mM/WN) @muy From ille uplbzy ank AQA. F. M. sElGLE Oct. .28, 1930.

METHOD FOR TRANSFORMING ANDIDI STILLING HYDROCARBONS Original Filed July 16, 1920 5 Sheets-Sheet 5 Patented Oct. 28, 1930 UNITED STATES Donn-TE ANTOINE FaANors MARiUs SETGLE, oF Panis, IRANCE'- 'l METHOD Fon TBANSFORMING AND DIs'rILLIirG Inmac(tumorsis.Iy l

originalfapplicauon mea July 1e, 1920, serial No. 396,767, alla in France July 17, 191B. Divided this application led January 14, 1926.v Serial No. 81,144.

(GaENTEn UNDER THE rnovrsrons or THE Acr or Manca a, 1921"?, 11'sur.,1.1..-'13'1'11'5` 'l I have led application for patent in* France July 17, 1918; July 25, 1918, and.

March 6, 1919, respectively, granted May23, 1921;,April 8, 1921, and January 23, 1922, under Nos. 524,901, 522,897 and 535,287; Germanyiled July 15, 1920, granted F eb'- ruary 22, 1927, under No. 445,657; Great Britain filed February 24, 1921, granted August 24, 1922, under No. 185,140; Argentine l lo Republic filed February 2, 1923, granted July 14, 1923, under No. 20,271; Belgium led December 24, 1921, ranted December 31,

1921, under No. 300,5 5'; Italy filed July 6,'

1920, granted November 5, 1921,. under No. 188,267; Mexico filed May 6, 1921, granted May 13, 1921,' under No. 20,306; Poland filed January 14, 1922, granted October 30, 1926, under No. 5,899; Rumania filed January 4, 1922, granted same date under No. 7,249; Czechosl )vakia filed December 21, 1921, granted Ma 5, 1924, under No. 14,064; Turkey filed Fe ruary 27, 1923, granted September 26, 1923, under No. 20.

This invention described in this application whichis a division of application No. 396,767 filed July 16, 1920, (Letters Patent No. 1,57 2,691) relates to an improved method for efecting in a practical and economical manner the regular and intensive vaporiza-l tion and the subsequent transformation` of certain hydrocarbons in the crude or the residual state such as mazout, heavy oils derived from peat, mineral oil, schist, lignite and other by-products of like chemical cornposition for instance heavy rosin oils.

The invention has for its purpose to obtain the following products in adjustable proportions: (1) hydrocarbons of a more or less light and inammable 'nature which can have 40 a considerable market value; especially asafueljor automobile or aeroplane engines; A(2) 'very heavy hydrocarbons of a more or. less fatty character which can be employed to advantage for the lubrication of numerous machines; (3) a high grade gas of the same kind as oil gas already employed either for improving the. quality of producer gas or for the lighting ofrailroad cars and of :factories and small towns.

v:so This high grade gas, in asuciently com- .way of example group of apparatusl c',

. 9, respectively.

a second set comprising theapparat G, H, I,`-.L, N and their accessorie pressed state, constitutes alsoa fuel which?? can be conveniently and advantageouslyv employed in engines for tramwaysfmotor coaches and the like. y" i .The method according to the invention can be carried out by means of an vimproved in l .stallation comprising various apparatus as more fully described hereinafter.`

In' the accompanying drawings givenA yby Fig. 1 is a general diagrammaticalplan*6o View of'f an installation in accordance/with the present invention. f Q Fig. 2 is an elevation view of vairstl grou of apparatus forming a part of' said instai lation. V Fig. 3 is an elevation view of asecond Fig. 4 is a longitudinal section of a retort.

. Fig. 5 is a cross section thereofalong they() line -d', Fig. 4. .I v

Fig. 6 is a cross section'thereof".alongthe line c-c, Fig. 4. l

' Fig. 6a is a detail in cross section of afplug for said retort. 75. Figs. 7 and 8 are elevational views of the" openings provided in the wall ofthe retort.

Fig. 9 is a longitudinal secti n of a cooling and expanding apparatus. y i i' Figs. 10 and 11 are cross ysections offthe ,'80 same along the lines N-N and,'M--M,"VFig.""

Fig. 12 isperspective detailuview portion of the interior of a; retort;

'and their accessory parts, which, is; separated by way of precaution Iby the wal'flrolin ai a The first series of apparatu' mpri s, o nem ,or'more retorts B (Figs. 1an 2) ;;Y eaclij""re `tort is composed of severalf;elerielnt the shape of a prism or afhollfow rf'solid :cylinder or like vform and inside jvrhicl`1fis,A

provided a coil shapedjcon` uithavingjcir culating therein the heavyjfjhydrocarbons undertreatment. The latterare `vpreviously raised to a temperature of about jto`180 C., thisbeng readily eecte'dlloy` the use 'ot 10o the heat of the burnt gases leaving the retort.

In the example shown, the retort B is composed of three elements A2, B2, C2, which are placed end to end, and one upon the other if Aspace which is divided by cross partitions connecting the two walls into five annular passages e stopped by a longitudinal partition u and placed in communication by means of orifices 1- situated alternately on one side of the partition u, so as to form a coil shaped conduit. This construction is clearly illustrated in Fig. 12 in which the direction of low of .the hydrocarbon gases is shown by the arrows 5.

In the outer wall of each of the three elements are disposed three elongated rectangular openings y, z (Fig. -6) one of which,`shown at the top of Fig. 6 and in front view in Fig. 7, shows the partition u at its middle part. These openings give access to the interior of the annular passages e for inspection and cleaning of the latter when desired or for disposing therein- 4at certain points metal straw or turnings (iron, aluminium, etc.) granulated metal or the like, adapted to aid in the treatment of the hydrocarbons. A

The said orifices are normally closed by Stoppers having a corresponding shape (Fig. 6a) and held in place by bolts or by arched closing members whereby they can be easily removed and re laced.

The elements 2. B2, C2 which are situated `in line and coaxially are connected together at the ends and spaced apart from one another by six cylildrical tenons g (Figs. 4 and 5), one of which is hollow and 'aiords communication between the coil portion adjacent elements A2,B2, C2.

The whole apparatus lies on its supportl ing frameby means-of the base portlons 'v (Fig. forming part of the outer walls and secured to the frame by bolts or screw spikes.

The retort which has just been described is operated in the following manner.

At the inlet end, is disposed a projection device A (Figs. 1 and 2) which projects axially into the central conduit or furnace of the retort and in the direction of the straight arrow 2, a stream of flame formed by gasiied or atomizedfuel which burns while mixing with the outer air which is automatically introduced (as shown by the curved arrows 1) through the spaces between the successive elelments of the retort (Fig. 4) and produces a greater or lessjdegree of heat in the retort according to `the force of projection and the density of the saidfstream' of flame.

of the The hydrocarbon which is to be treated is delivered into the coil conduit e, through the orifice f (Fig. 4) and passes successively through the whole series o convolutions of the three retort elements, being discharged atv the other end f of the coil passage after having followed the general direction shown by the arrows 5 and being submitted to a gradually increasing heating action.

The metal turnings placed in the coil conduit will .divide and so to speak laminate into very fine streams the hydrocarbons and already more or less gasiied vapor is produced in the first portion of this circulation, and the well known action of superheating upon the hydrocarbon vapors now becomes much stronger for a given temperature and also sufficiently easy to regulate. O'n the other hand since the iron 4and aluminum `turnings have an active though small capacity for absorption of atoms of carbon andhydrogen at the respective temperaturesor` 650 and 450 C., this will ai'ord another cause for the rupture of chemical equilibrium of the hydrocarburated molecules, which cause 'of rupture will be added in an etlicient manner ,to that resulting from the methodical superheating to whose elects these same molecules are subjected at the said respective temperatures by reason of the successive passage of the same through the layers of aluminum turn. ings at about 450 and then through the layers of iron turnings at about 650 C.

However, as is well known to specialists, all systems in chemical equilibrium will be submitted to a transformation in a determined sense by reason of the variation of a single one of the factors of this equilibrium lmixture issuing from the retort is substantially the same as that'of the raw hydrocarbons.

The installation shown comprises also two primary gas cooling and expanding apparatus E and G (Figsl and 3).

, One of the characteristic 4features of the apparatus resides in the fact that a sudden but purposely incompletel cooling ofthe hydrocarbon vapors or gases `isObtained therein by the use as a ,cooling medium, not of a current of cold air or waterlas in the standard types of refrigerators for or vapors at high temlno peratures, but of water in ebullition at a va'- riable-temperaturef- 1 y f i YEach cooler-expander-(Figs. 9, andll): comprises an louter:re'ceptacleor` iron or. steel plateyA, and ay secondreceptacle more or less permanently secured in the middleof this latter. This inner receptaclecomprises three cylindrical or truricatedcone` shaped portions preferably of cast iron, steelor the tubes'fz/2 and z2 Iand the `central` cylinderA4 are assumed asy entirely'ffilled with water already heated to the desired boiling temperature, the latter vbeing :obtained by varying the pressure and .observing thefsame by means of the pressure gauge I2 (Fig. 9). n j

- `".{Xvalve orcock (notshown here) is know openedftoconnectiV the tubeE2 for instance with the dischargepipingfofaretort such like, or of metal sheet (iron o1; ,c ipper.). Landasthatf'described above lin which a certain welded togetherv in ordent'provide a sufli# eient lat'conductivity for the entire assem` blage of these three Parts. Q s

These three portions comprise the cylinder B4* havingat its base a circular flange which is bolted to the bottom Yof thefou'terreceptacle or digesterA; the truncated coneshaped por- 'tin'B which connects the said cylinder B4 to theupper truncated cone shaped part C4, this beingclo'sed at the lower part by a disk` having-therein a series of orifices near the periphery (Fig. 9) and finally the cylindrical portion A4 wlnchis in communication with'the outer receptacle Asby means'of two' horizontal connecting tubes y2 anda?. This cylinf drical portionA is closed at the 4top by a metal stopper .s which is permanently yheld in place by means of four screws cooperating with the ourlugsor shoulders s. y

Upon the bottom of theouter receptacle A3 are bolted the flange of the cylinderfB4 and a sufficiently thick disk of cast iron,-steel or bronze havingiintegral therewithl the cen# tral tube E2. On this same. disk are screwed two cocks F,2 and F3 one of which carries a pipe F4. This pipe extends up to 4a. certain e1 sure that the level of theliquid ghi'I Wthinthe part B5 and serves to make 'therein r'is above its k endf'mf 'i In thef'anular space between the central "receptacle A* andthe inner wall bf the cone C* are'disposed three metal plates m2 which rest upon suitable supports'az:3 (Fig. 9). Two

of'these plates have a transverse cut out'portion whereby theycan be inserted belowvthe connecting vtube y. I'The three plates m2 are staggered relatively tov those of the vadjacent plates, so that :the path of the gases through said holes is that shownby thearrow (Fig`.`9)

The operation of placing the plates or disks m2 and the disk rz'is'carried out 'atfthe same time as the filling; ofl thev 'spaces' betweenthe said threedisks andthe upper `diskbyiron turnings, granulatedljcast iron or` like ma.' terial adaptedforzthe' thermo-chemicaltreat- [ment of the heavy hydrocarbons to be treated.

When these operations are completedgthze cfap 1D? hermetically, securedl ytoV theftruncated cone 'shapedportionfC g .The operatlonof the said cooler-expander is asvfollows:` tif g For thersake*ofdclearness the complete' digester formed by the receptacle A8, the' two I n l* v 'the saidf'gases-orvapors.' provided with apertures 'which f are so dis- Aposed that the-apertures of'onefplate vare l i'lhefpowerfl y duced' are ydirected into the central conduit A o r furnace of the retort B. As previously fstatedfsaidfretort may arran V"edeither .liorizont'ally,l asshown,y or kvertical yo quantity of mazout or astatki is treated;

'lhehydrocarbon vapors thus admitted by the' tube E2 will nowbe caused to expand in the portions 'B4 andB5 of the cooling and expanding apparatus and will circulate through the sets of staggered orifices as shown by the `arrows (Fig. 9) and through the entire .mass'of iron t'urnings, granulated cast iron aswell as the innersurface ofthe cylinder Af areV in directcontact with the water which has beengpreliminarily leated to its Vboiling temperature. "Now,4 asis well known, the

vaporizationof water'absorbs,.in a practically instantaneous manner,' at least ten times vthe amount of heat that this same quantity Vof water would absorb more or'less slowly when passing for instance from 10 to 60 Clas itis the case for `mallyfof the customary'coolking dances;

passingl 1through the coolingjand expanding apparatus, the gases or vapors discharged"by----' the retort willbe incompletly but very rapidlycooled',` thus giving up a considerable proportion of their heat; which will be instantaneously absorbed; byfthe instantaneous vapoiization ofI a. corresponding quantity'of i water already at its boiling temperature.

This results in a partial depolymerization of paratusfarranged yas follows :I

' 'The liuidy fuel of -cheap qualityv which The-installation comprises additional 'appressure tankA (Figsl and2) by the pipe a.

' Said `fuel is led bythe pipe af into agasifying.

apparatus A of' a standard ltyp`e,"w fhich may ers"1 supplied withyproducerfgas yor theI like. ame or fiames' thus proi'neliiie'd position.

f 'rhejgases of combustin whiich `'51eme' the', *heating 'conduit' ofthe retort "B'vvill travelin zigzag path i (Fig. 2) through `the double is )used-for eating .the retort is'delivered'intoia rectangular chamber of a recuperator of heat, wherein they pass according to the arrows 3 and 4 and they will be successively cooled upon the outer walls of the two heat exchang- -ing members C and O and they are Iinally dis- .introduced by the pipe b into the retort B.

The more or less superheated hydrocarbon. vapors escaping from the retort B are conveyed by a pipe E3 through the partition wall d d to the centralintake pipe E2 of the irst cooler-expander E (Figs. 1 and 3) the construction of whichv has been explained above.

The'uncondensed portion of the said partially gasied vapors is` then taken oi apparatus G into the apparatusthrough the pipe E* from the upper outlet D of said apparatus E by means of the motor pump F which delivers the gases through a pipe f to a second cooler expander G. The uncondensed vapors are discharged from the latter apparatus through the pipe g directly into the final cooling apparatus I-I, I, I (Figs. 1 and 3) whence the noncondensable gases p'ass through the pipe Z to the scrub-- ber and the purifier L, L and are finally collected in a gas holder.

The remaining portion of the gases and vapors which are'led from the to ofI tle chieily due cin the rst place to an intense and very sudden cooling and secondly to the rather strong expansion or reduction of prcssure to which -the hydrocarbon gases or vapors are submitted when passing successively'through each of the said cooler-expanders.

On the other hand, this rupture of chemical equilibrium is further caused by the action of the successive layers of metalscrapil1gs or turnings which are placed in any desired quantity withvithe inner receptacle C4 (Fig. 9) of each cooleixpander, upon the removable plates :122.

In order to properly specify this action it will be necessary to explain how and ,for .which reason the cooler-expanders E and G (Figs.` 1. and 3) operate at dilerent inner temperatures and pressures.

The question will be simplified by considering only the case in which, for instance,

the ressure of the steam, and therefore that of t e feed water to be vaporized, will b e 5 kilogrammes per square centimeter in both the outer receptacles or chambers of these two cooler-expanders, a difference ofd80 C. being however obtained between their respective inner temperatures due to the fact that the outer receptacle of the apparatus E- is first illed with a saturated solution of chloride of calcium up to the normal level.

Under these conditions of operation, the more or less gasified vapors willescape from the retort at a temperature of, for instance, 650 C. and a pressure of 1.2 kilogrammes per square centimeter are then brought very suddenly to a theoretical temperature of 235 C., but a practical temperature of 260 \`Cand-also^to a pressure of about 4 hecto- (Figs. laand 3) is cooledv to a rather low temperature by passing within a cooler having cold water circulated therethrough, this water being brought by means of the pipe fm.` into the lower partof the tank I and leaving this latterthrough the pipe fm. whose outlet is-situated almost at the upper edge 'of' the said tank.

It will be seen that the water which is supplied as cold as possible through the pipe m, reaches theplpe tm. in a more or less Warm state and is'sucked through the latter by means ofa motor ump N (Fig. 1) which delivers it-through t e pipe n into the heat exchanger 0, and thence arrives, through the pi o and its two branches o? and o', and su stantially at the boiling temperature into the outer chambers .of the two cooler-- expanders G and E (Figs. 1 and 3) from it is nall discharged by the pipes r* (Fig. 3l' in the state of saturated steam;

In "connection with the operation of the above described and more particularly A res ct to the cooler-'expanders E and G, it be noted that in the latter apparatus, the rupture of chemical equilibrium is grammes per squ ecentimeter, by their passage through the first mer-expander E whence the motor pump F draws ut\the\ same and compresses them while at the same y time heating them to a slight degree; in this mannerthey are submitted to a second and still considerable reduction of temperature and pressure by flowing through the second cooler-expander G, entering therein -at about 300 C. and under a pressure of 9 hectogrammes perl square centimeter and leaving the same at about 160 C. under a pressure of about 2 to 3 hectogrammes.

The different temperaturesand pressures of the hydrocarbons under treatment are controlled by meansof fixed or movable pyrometers and pressure gauges disposed at various suitable points for instance at s', s', s* (Figs. 2 and 3). The said temperatures and pressures are regulated by making the necessary variations of the discharge orifices of the valves or cocks disposed upon the piping' connecting the di'erent apparatus, especially at b', Ea and E* (Figs. 1 and 2) In short, when passlng successively through both cooler-expanders E and G, the

fno

to 160 C. However, as already explained,

the iron and aluminium turnings aid in producing the rupture of chemical equilibrim of the said molecules at the respective temperatures ofabout 450 and 650 C., on the other hand, thin copper turnings have an active af- A Y res onding to those indicated finity for hydrogen between 300. C. and 500 C. and ferro-nickel turnings have a `double aiiinit for carbon and hydrogen between 200 and 350 C.

In consequence, the successive layersof the above mentioned metal turnings'or scrapings are to be distributed according to the thermochemical data above set forth, in the inner receptaclesof the two cooler-expanders.

Each pair of cocks p, p', g, g (Fi 3), cor- 13g2 and F3 b in ig. 9, serves to control the idling operation and to drain out the lowerportion of thek innerrreceptacle of one of the apparatus E and G (Figs. 1 and 3'). 7

' The very heavy condensed hydrocarbons drop into this portion, and are condensed by reason ofthe intense cooling action successively produced in the first and then in the second of the said cooler-ex anders.

The cock K is employed or the discharge of the light and inflammable hydrocarbons which are condensed in the final cooling apparatus H, I (Figs. 1 and 3).

In certain cases where forinstance it will be found advantageous to increase the output of liquid and very inflammable fuel to the `deteriment of the high grade gas, the

above described plant can be completed by one of the systems now in use for `the industrial hydrogenationfofrolive oil, linseed oil, fish oil and the like as well as hydrocarbons, by meansof usual metals employed as ncata.d

lyzers. v h For this purpose, there may be provided a .Y simultaneous suction and a ve intimate mixture of the vapors discharge from the a paratus E (Figs. 1 and 3) with a portion o? the high grade gas stored in the gas holder and to which hydrogen can be added if required, the perfect mixture thus obtained is thus delivered into the inner receptacle of the However, in industrial practice, it may happen that an economical supply can only be o tained of crude hydrocarbons such as Ynaphtha or crude oil. In this case it is first required to effect a previous separation of the hea hydrocarbons by a mere distillation whiizh can be very easily carried out by means lof the installation represented Figs. 1, 2

I and 3, but exclusive of the apparatus for puri- -fying and collecting the gas which are not required here. It is of course understood that the operation of the installation thus transformed should be carried out at temperatures suitable for the new and comparatively easy result to be here obtained and not With the use of the temperatures previouslymentioned for obtaining the depolymerization of the hydrocarbons. A

The ,invention is not restricted to the details of execution shown or describedwhichy heating stage which consists in heating, in a very regular and gradual manner, the vapors formed during said preheating stage and the gaseous hydrocarbons produced during said main heating stage being successively submitted to the action of catalyzers, the maximum temperature being substantially comprised between 500 C. and 700 C. and the pressure being maintained below substantially 1.2 kilogrammes per square centimeter,

and a number of successive cooling stages to which the mixture of gases and vapors issu- -mg' from said main heating stage are subjected the cooling medium used in the first cooling stage being boiling water at a predetermined superatmospheric pressure so that the sudden drop in the temperaturev of said gases and vapors through said first cooling stage be substantially comprised between 250 C. and 450 C. A

. 2. In the method as claimed in claim 1 the further feature residing in/that said mixture of gases and vapors is subjected, during said cooling stages, to the -action of other cata.

lyz'ers having ,respectively their specific action at the temperature in said stages.

3. In the method as claimed in claimlthe further feature residing in -that said mixture of gasesand'vapors is subjected, during said Y cooling-stages, to the action of other catalyzers having respectively their specific action at the temperature in said stages, the catalyzers used respectively in said main heating stage and in said cooling stages being adapted for the conversion of the raw hydrocarbon vapors into condensable lighter hydrocarbons, the percentage composition in carbon and hydrogen of said latter hydrocarbons being substantially the same as that of the raw hydrocarbon.

4. In the method as claimed in' claim 1, the

further'featgre residing in that the gases g and vapors resulting from each cooling stage are further submitted to a reheatin jand com- .pnes'sion stage before they are su mitted to the following cooling' p z stage car 5. Method for the transformation of heavy hydrocarbons which comprises aA heating which consists in heating said hydroons by causing the `same to circulate around a central furnace according to a path formed of successive and adjacent con-. volutions in planes at right angles to the direction of circulation of the heating gases within, said furnace and alternately in opposite direction in the successive convolutions, the longitudinal direction of the hydrocarbon iiow bemg opposite that of said heating gasesA through the furnace, the gases and vapors produced along Isaid path iiowing through catalyzers res ect'ively disposed at successive points thereo and having respectively their maximum action at the temperatures prevailing at said successive points, the maximum temperature being substantially comprised between 500 and l700 C., and the pressure being maintained below substantially 1.2 'kilogrammes per square centimeter, and 4a Amain heating stage are subjecte number of successive cooling stages to which thl mixture of gases and vapors issuing from said main heating stage are subjected, the cooling medium used in the first cooling stage being boiling water at a predetermined su ratmospheric pressure so that the sudden rop in the temperature of said gases and vapors through said lirst cooling stage be substantially comprised between v250 C. and 450 C. 6. Method for the transformation of heavy hydrocarbons which comprises a preheating stage for vaporizing the raw hydrocarbons, a main heating stage which consists in heating, in a very regular and gradual manner, the vapors formed during said preheating stage, substantial] up to 450 C., submitting the gaseous hy rocarbons thus produced to the catalytic action of aluminum and further heating the resulting h drocarbonsi u to a maximum tem rature A'letween 500V` `:and 700 C. and su mitting them to the catalytic action of iron, the maximum pressure of said gaseous hydrocarbons being substantially 1.2 kilogrammes pg' square centimeter, and two successive coo g stages, to which the mixture of gases and vapors from'said I by means of bollmg water successively at a temperature between 250 C. and 300 C., and between C. and 200 C., respectively inthe presence of copper and ferro-nickel.

In testimony whereof I have. signed my name to this-specification.

MURE ANTOINE mllols .ANUS SElGl-E. 

